6364-05-2Relevant academic research and scientific papers
CO2-tuned highly selective reduction of formamides to the corresponding methylamines
Chao, Jianbin,Guo, Zhiqiang,Pang, Tengfei,Wei, Xuehong,Xi, Chanjuan,Yan, Leilei
supporting information, p. 7534 - 7538 (2021/10/12)
We herein describe an efficient, CO2-tuned and highly selective C-O bond cleavage of N-methylated formanilides. With easy-to-handle and commercially available NaBH4 as the reductant, a variety of formanilides could be turned into the desired tertiary amines in moderate to excellent yields. The role of CO2 has been investigated in detail, and the mechanism is proposed on the basis of experiments.
1,2-Difunctionalization of Aryl Triflates: A Direct and Modular Access to Diversely Functionalized Anilines
Cho, Seoyoung,Wang, Qiu
supporting information, (2020/02/28)
ortho-Amino difunctionalization of aryl triflates has been achieved via a three-component reaction. The cascade reaction proceeds through a zincate base-mediated deprotonative formation of a reactive aryne intermediate, in situ nucleophilic addition, and coupling with electrophilic partners. This strategy leverages the advantageous reactivity of organozincate intermediates, enabling the installation of various functionalities such as amine, azide, oxygen, sulfur, halide, alkynyl, aryl, vinyl, and alkyl groups in a modular manner for the synthesis of diverse aniline skeletons.
Nickel-Catalyzed Decarboxylation of Aryl Carbamates for Converting Phenols into Aromatic Amines
Nishizawa, Akihiro,Takahira, Tsuyoshi,Yasui, Kosuke,Fujimoto, Hayato,Iwai, Tomohiro,Sawamura, Masaya,Chatani, Naoto,Tobisu, Mamoru
supporting information, p. 7261 - 7265 (2019/05/16)
Herein, we describe a new catalytic approach to accessing aromatic amines from an abundant feedstock, namely phenols. The most reliable catalytic method for converting phenols to aromatic amines uses an activating group, such as a trifluoromethane sulfonyl group. However, this activating group is eliminated as a leaving group during the amination process, resulting in significant waste. Our nickel-catalyzed decarboxylation reaction of aryl carbamates forms aromatic amines with carbon dioxide as the only byproduct. As this amination proceeds in the absence of free amines, a range of functionalities, including a formyl group, are compatible. A bisphosphine ligand immobilized on a polystyrene support (PS-DPPBz) is key to the success of this reaction, generating a catalytic species that is significantly more active than simple nonsupported variants.
Biphenyl sulfonic acid ligands for catalytic C-N cross coupling of aryl halides with anilines and secondary amines
Wittel, B?rbel,Vogel, Till,Scharl, Heiko,Nerdinger, Sven,Lehnemann, Bernd,Meudt, Andreas,Snieckus, Victor
, p. 4583 - 4593 (2018/07/31)
The use of two biphenyl sulfonic acid ligands for the catalytic C-N cross coupling of aryl halides with anilines, 3-aminopyridine, and secondary amines is reported. Our results represent a significant improvement compared to state of the art methods especially with regards to the removal of palladium.
Direct Borylation of Tertiary Anilines via C-N Bond Activation
Cao, Zhi-Chao,Li, Xiao-Lei,Luo, Qin-Yu,Fang, Huayi,Shi, Zhang-Jie
supporting information, p. 1995 - 1998 (2018/04/16)
The first successful catalytic borylation of unactivated aromatic C-N bonds of tertiary anilines without the preactivation or any directing groups is demonstrated. The reactivity of both N,N-dialkylarylamines and N-arylpyrroles were investigated systematically, and the targeted products were furnished in moderate to good yields. The DFT calculation results indicated that the catalytic cycle is furnished via a five-membered cyclic transition-state due to the steric hindrance of the Ni/NHC catalytic system.
A General Palladium–Phosphine Complex To Explore Aryl Tosylates in the N-Arylation of Amines: Scope and Limitations
Choy, Pui Ying,Chung, Kin Ho,Yang, Qingjing,So, Chau Ming,Sun, Raymond Wai-Yin,Kwong, Fuk Yee
supporting information, p. 2465 - 2474 (2018/09/10)
The scope and limitations of the monoselective N-arylation of various amines by using aryl and hetaryl tosylates are presented. The air-stable and easily accessible Pd(OAc)2/CM-phos {CM-phos=2-[2-(dicyclohexylphosphino)phenyl]-1-methyl-1H-indole}catalyst system was able to deal with a wide range of aryl tosylate substrates as well as amine nucleophiles, including primary and secondary cyclic/acyclic aliphatic amines and anilines. NH-Bearing heterocycles such as indole, carbazole, pyrrole, 10-phenothiazine, and 10-phenoxazine were shown to be feasible coupling partners under this catalytic system. The described reaction conditions tolerate a wide range of functional groups and allow an array of aromatic amines as well as unsymmetrical amine products to be easily accessed from the various phenolic derivatives. Interestingly, this catalyst system even offers the opportunity to perform the reaction in water medium. We also report the intermolecular coupling of optically active α-central chiral amines with aryl tosylates without erosion of the enantiomeric purity.
Synergistic Catalysis of Ionic Br?nsted Acid and Photosensitizer for a Redox Neutral Asymmetric α-Coupling of N-Arylaminomethanes with Aldimines
Uraguchi, Daisuke,Kinoshita, Natsuko,Kizu, Tomohito,Ooi, Takashi
supporting information, p. 13768 - 13771 (2016/01/15)
A redox neutral, highly enantioselective coupling between N-arylaminomethanes and N-sulfonyl aldimines was developed by harnessing the efficient catalysis of P-spiro chiral arylaminophosphonium barfate and a transition-metal photosensitizer under visible
Three-Component Coupling Involving Arynes, Aromatic Tertiary Amines, and Aldehydes via Aryl-Aryl Amino Group Migration
Bhojgude, Sachin Suresh,Baviskar, Dnyaneshwar R.,Gonnade, Rajesh G.,Biju, Akkattu T.
supporting information, p. 6270 - 6273 (2016/01/09)
The transition-metal-free multicomponent coupling of arynes, aromatic tertiary amines, and aldehydes proceeding via the aryl to aryl amino group migration has been demonstrated. This protocol allows rapid access to ortho-functionalized tertiary amines in moderate to good yields. Moreover, activated ketones can also be used as the aldehyde component in the present reaction. The similarity of the aryl-aryl tertiary amino group migration with the Smiles rearrangement is striking.
Transition-Metal-Free, Potassium tert -Butoxide/Dimethyl Sulfoxide Mediated Amination between Tertiary Amines and Aryl Halides
Huang, Pei,He, Bang-Yue,Wang, Hui-Min,Lu, Jian-Mei
, p. 221 - 227 (2015/08/25)
A transition-metal-free, C-N bond-formation reaction between tertiary amines and aryl halides is reported. Under the optimal conditions, various aromatic and aliphatic tertiary amines react with aryl halides, including iodides, bromides, and chlorides, to give mono-aminated products, N,N-dialkylanilines and N-alkyl-N-arylanilines, in good to high yields. Based on the experimental results, the reaction is believed to occur via an aryne intermediate derived from the aryl halide.
Transition-Metal-Free, Potassium tert -Butoxide/Dimethyl Sulfoxide Mediated Amination between Tertiary Amines and Aryl Halides
Huang, Pei,He, Bang-Yue,Wang, Hui-Min,Lu, Jian-Mei
, p. 221 - 227 (2015/08/25)
A transition-metal-free, C-N bond-formation reaction between tertiary amines and aryl halides is reported. Under the optimal conditions, various aromatic and aliphatic tertiary amines react with aryl halides, including iodides, bromides, and chlorides, to give mono-aminated products, N,N-dialkylanilines and N-alkyl-N-arylanilines, in good to high yields. Based on the experimental results, the reaction is believed to occur via an aryne intermediate derived from the aryl halide.
